WO2016108375A1 - Procédé de production de précurseur de matériau actif positif et de matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration, et précurseur de matériau actif positif et matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration produits selon ce dernier - Google Patents

Procédé de production de précurseur de matériau actif positif et de matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration, et précurseur de matériau actif positif et matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration produits selon ce dernier Download PDF

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WO2016108375A1
WO2016108375A1 PCT/KR2015/007718 KR2015007718W WO2016108375A1 WO 2016108375 A1 WO2016108375 A1 WO 2016108375A1 KR 2015007718 W KR2015007718 W KR 2015007718W WO 2016108375 A1 WO2016108375 A1 WO 2016108375A1
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active material
concentration gradient
aqueous solution
lithium secondary
secondary battery
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PCT/KR2015/007718
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English (en)
Korean (ko)
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최문호
김직수
윤진경
전석용
정재용
성용철
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주식회사 에코프로
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Priority to EP15875469.7A priority Critical patent/EP3242348B1/fr
Priority to JP2017533200A priority patent/JP6722673B2/ja
Priority to CN201580071865.XA priority patent/CN107112516B/zh
Priority to PL15875469.7T priority patent/PL3242348T3/pl
Publication of WO2016108375A1 publication Critical patent/WO2016108375A1/fr
Priority to US15/630,014 priority patent/US10749205B2/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a method for producing a cathode active material precursor and a cathode active material for a lithium secondary battery exhibiting a concentration gradient, and to a cathode active material precursor and a cathode active material for a lithium secondary battery exhibiting a concentration gradient prepared thereby, more specifically, a heat treatment process thereafter.
  • the present invention relates to a cathode active material precursor and a cathode active material for a lithium secondary battery.
  • lithium ion batteries developed in the early 1990s have been widely used as power sources for portable devices since they emerged in 1991 as small, lightweight, and large capacity batteries.
  • Lithium secondary batteries are in the spotlight due to the advantages of higher operating voltage and significantly higher energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries using an aqueous electrolyte solution.
  • conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries using an aqueous electrolyte solution.
  • research on power sources for electric vehicles that hybridize internal combustion engines and lithium secondary batteries has been actively conducted in the United States, Japan, and Europe.
  • a lithium ion battery is considered as a large battery for an electric vehicle from an energy density point of view
  • a nickel hydride battery is still used from the viewpoint of safety.
  • the biggest challenge for lithium ion batteries for use in battery vehicles is their high cost and safety.
  • a cathode active material such as LiCoO 2 or LiNiO 2 which is currently commercially used
  • when a battery in an overcharged state is heated at 200 to 270 ° C. when a battery in an overcharged state is heated at 200 to 270 ° C., a sudden structural change occurs, and the reaction causes oxygen to be released in the lattice due to such a structural change.
  • the crystal structure is unstable due to de-lithography during charging, which has a disadvantage in that thermal characteristics are very poor.
  • LiNi1-xCoxO 2 (x 0.1-0.3) material, in which a part of nickel was substituted with cobalt, showed excellent charge and discharge characteristics and life characteristics, but thermal safety problems could not be solved.
  • the composition and production of Li-Ni-Mn-based composite oxides partially substituted with Mn having excellent thermal stability at Ni sites or Li-Ni-Mn-Co-based composite oxides substituted with Mn and Co are known. Recently, Japanese Patent No.
  • 2000-227858 discloses a positive electrode active material having a new concept of dissolving a transition metal to LiNiO 2 or LiMnO 2 to form a solid solution by uniformly dispersing Mn and Ni compounds at an atomic level.
  • a transition metal to LiNiO 2 or LiMnO 2
  • LiNi1-xCoxMnyO 2 (0 ⁇ y ⁇ 0.3) is Compared with Ni and Co-only materials, it has improved thermal stability, but still does not solve the thermal stability of Ni system.
  • the coating amount is less than 1 to 2% by weight compared to the positive electrode active material
  • the coating layer is known to form a very thin film layer of several nanometers to suppress side reaction with the electrolyte, or when the heat treatment temperature after coating is high.
  • a solid solution may be formed on the surface of the powder particles to have a metal composition different from that inside the particles.
  • the surface layer combined with the coating material is known to be tens of nanometers or less, and there is a drastic compositional difference between the coating layer and the bulk of the particle, which reduces the effect of long-term use of several hundred cycles.
  • the effect is halved due to incomplete coating in which the coating layer is not evenly distributed on the surface.
  • a patent for a lithium transition metal oxide having a concentration gradient of a metal composition is proposed in Korean Patent Application No. 10-2005-7007548.
  • this method can synthesize the metal composition of the inner layer and the outer layer differently during synthesis, but the metal composition does not change gradually gradually in the resulting positive electrode active material. Gradual gradient of the metal composition can be achieved through the heat treatment process, but at a high heat treatment temperature of 850 ° C. or higher, a gradient of concentration rarely occurs due to thermal diffusion of metal ions.
  • the powder synthesized by the present invention does not use ammonia, which is a chelating agent, the powder has a low tap density and is not suitable for use as a cathode active material for lithium secondary batteries.
  • this method is difficult to control the amount of lithium in the outer layer when using a lithium transition metal oxide as the inner material is poor reproducibility.
  • Korean Patent Application No. 10-2004-0118280 proposes a double layer structure having a core-shell structure.
  • a CSTR reactor is used to report a material having high capacity and thermal stability by combining a positive electrode composition having a high capacity characteristic in the core and a positive electrode composition having excellent thermal stability in the outer shell.
  • this patent also has a problem in that it is difficult to form a structure having a continuous concentration distribution between two interfaces due to diffusion of metal elements at the interface where the inner core and the outer shell meet.
  • the present invention provides a method of manufacturing a positive electrode active material precursor for a lithium secondary battery having a concentration gradient layer that can exhibit an intended continuous concentration distribution even at the interface where the core and the outer shell meet to solve the problems of the prior art as described above,
  • An object of the present invention is to provide a production method and a cathode active material precursor and a cathode active material produced thereby.
  • the present invention to solve the above problems
  • the aqueous solution for shell formation was prepared, and the chelating agent aqueous solution, the basic aqueous solution, and the core forming aqueous solution and the shell forming aqueous solution were continuously added simultaneously to the reactor, so that the concentration of nickel manganese cobalt was gradually increased on the surface of the barrier layer.
  • a fourth step of obtaining a precipitate constituting the concentration gradient layer changed to;
  • a sixth step of heat treating the dried precipitate It provides a method for producing a cathode active material precursor for a lithium secondary battery having a concentration gradient layer comprising a.
  • the barrier layer forming aqueous solution includes Ni and Mn.
  • the aqueous solution for barrier layer formation is characterized in that it comprises Ni and Mn in a molar ratio of 30:70 to 70:30.
  • the aqueous solution for barrier layer formation is characterized in that it comprises Ni and Mn in a molar ratio of 50:50.
  • the aqueous solution for forming a core and the aqueous solution for forming a shell are mixed in a separate preliminary reactor, and the mixed solution is added to the reactor. At the same time it is characterized in that the continuous feeding.
  • Method for producing a cathode active material precursor for a lithium secondary battery having a concentration gradient layer is continuously and simultaneously in the reactor while mixing the shell forming aqueous solution, the chelating agent aqueous solution, and the basic aqueous solution between the fourth step and the fifth step. It is characterized in that it further comprises a 4-2 step of obtaining a spherical precipitate which is added to form a shell layer.
  • the present invention also provides a cathode active material precursor for a lithium secondary battery having a concentration gradient layer prepared by the method for producing a cathode active material precursor for a lithium secondary battery having a concentration gradient layer according to the present invention.
  • the barrier layer is characterized in that the thickness is less than 2.0 ⁇ m at 0.01 ⁇ m or more, or less than 20% at 1% or more relative to the particle volume.
  • the size of the primary particles of the positive electrode active material precursor for a lithium secondary battery having a concentration gradient layer according to the present invention is characterized in that 10 to 40% less than the size of the primary particles of the positive electrode active material precursor of the same composition not containing a barrier layer do.
  • the present invention also provides
  • Heat treatment at 750 to 1000 ° C. for 10 to 25 hours in an oxidizing atmosphere of air or oxygen; It provides a method for producing a cathode active material for a lithium secondary battery having a concentration gradient layer comprising a.
  • the present invention also provides a cathode active material for a lithium secondary battery having a concentration gradient layer prepared according to the present invention.
  • the present invention is a method for producing a positive electrode active material precursor and a positive electrode active material for a lithium secondary battery having a concentration gradient, characterized in that it comprises a barrier layer between the core having a constant concentration and the shell portion having a concentration gradient, according to the present invention
  • the prepared cathode active material has an effect of showing a continuous concentration distribution intended for design even at the interface where the core and the outer shell meet, even if diffusion of the transition metal between the core and the shell occurs.
  • Figure 1 shows the results of measuring the SEM photograph of the active material particles prepared in one embodiment and comparative example of the present invention.
  • Figure 2 shows the results of measuring the concentration of the transition metal in the active material particles prepared in one embodiment and comparative example of the present invention.
  • Figure 3 shows the results of measuring the charge and discharge characteristics of a battery including the active material particles prepared in one embodiment and comparative example of the present invention.
  • Figure 4 shows the result of measuring the residual lithium of the battery including the active material particles prepared in one embodiment and comparative example of the present invention.
  • a reactor for forming a core of 2.5M concentration in which a nickel sulfate, cobalt sulfate, and manganese sulfate molar ratio was mixed at a ratio of 90: 10: 0, was 2.41 L / hour, and an aqueous 28% concentration ammonia solution was 0.29 liter / hour.
  • 25% sodium hydroxide aqueous solution was supplied for pH adjustment so that the pH was maintained at 11.2.
  • Impeller speed was adjusted to 350rpm. 60.5 L of the resulting aqueous solution for core formation, ammonia and sodium hydroxide were continuously added to the reactor. In consideration of the reactor capacity, the reaction proceeded while the supernatant was discharged at a predetermined time.
  • a 2.5 molar concentration of aqueous solution for forming a barrier layer of nickel cobalt sulfate manganese sulfate was mixed at a ratio of 50: 0: 50, and the aqueous solution for forming the barrier layer was 2.41 L / hour, and an aqueous 28% concentration of ammonia was used.
  • the barrier layer-forming aqueous solution, ammonia and sodium hydroxide were 3.7 L.
  • a concentration gradient layer of 2.5M concentration of nickel sulfate, cobalt sulfate, and manganese sulfate in a ratio of 19.4: 24.3: 56.3 to match the molar ratio of nickel sulfate, cobalt sulfate, and manganese sulfate 65:15:20.
  • An aqueous solution was prepared and mixed with a 2.5M concentration core aqueous solution in which the nickel sulfate and cobalt sulfate molar ratios were mixed in a 90:10 ratio in a separate stirrer in addition to the batch reactor.
  • an aqueous ammonia solution containing 2.41 L / hour and 28% concentration of a shell forming aqueous solution for forming a shell mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a molar ratio of 40:20:40 was added to a batch reactor.
  • the solution was added at a rate of 0.29 L / hour and the sodium hydroxide solution was added at a pH of 11.2.
  • a spherical nickel manganese cobalt composite hydroxide precipitate was obtained from a batch reactor.
  • the precipitated composite metal hydroxide is filtered, washed with water and then dried in a 110 °C hot air dryer to obtain a powder.
  • step 6 the composite metal hydroxide obtained in step 6 was mixed with lithium hydroxide and heat-treated at 810 ° C. for 10-20 hours to obtain a cathode active material for a lithium secondary battery.
  • a positive electrode active material for a lithium secondary battery was obtained in the same manner as in Example 1 except that the concentration gradient layer was formed first and the barrier layer was formed after the core layer was formed.
  • a cathode active material for a lithium secondary battery was obtained in the same manner as in Example 1 except that a core layer, a concentration gradient layer, a shell layer, and a barrier layer were formed at the outermost shell layer.
  • a cathode active material for a lithium secondary battery was obtained in the same manner as in Example 1 except that the barrier layer and the shell layer were formed without forming a concentration gradient layer after the core layer was formed.
  • a positive electrode active material for a lithium secondary battery was obtained in the same manner as in Example 1 except that the particle average composition was set to Ni: Co: Mn of 64:19:17.
  • a lithium secondary battery positive electrode active material was obtained in the same manner as in Example 1 except that the particle average composition was designed such that Ni: Co: Mn was 66:17:17 and the heat treatment temperature was performed at 920 ° C.
  • the first precursor aqueous solution of 2.5M concentration mixed with nickel sulfate, cobalt sulfate, and manganese sulfate molar ratio of 90: 10: 0 ratio was 2.41 L / hour, and the aqueous ammonia solution of 28% concentration was 0.29 liter.
  • the reactor was continuously fed at / hour.
  • 25% sodium hydroxide aqueous solution was supplied for pH adjustment so that the pH was maintained at 11.2.
  • Impeller speed was adjusted to 350rpm. 63.87 L of the prepared first precursor aqueous solution, ammonia and sodium hydroxide solution were continuously introduced into the reactor.
  • the concentration of 2.5M in which the nickel sulfate, cobalt sulfate, and manganese sulfate molar ratio was mixed at a ratio of 19.4: 24.3: 56.3.
  • aqueous solution for forming a gradient layer After making an aqueous solution for forming a gradient layer, weighing 8.016 kg of 2.5M aqueous solution in which the second-stage nickel sulfate, cobalt sulfate, and manganese sulfate molar ratios were mixed at a ratio of 90: 10: 0 in a separate stirrer in addition to the batch reactor.
  • the aqueous solution for forming the third concentration gradient layer was added to the second aqueous solution.
  • An aqueous 28% concentration of ammonia was added at a rate of 0.29 L / hour and the sodium hydroxide solution was maintained at a pH of 11.2. At this time, the introduced precursor solution, ammonia and sodium hydroxide were 10.06L.
  • a fourth precursor aqueous solution mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a molar ratio of 40:20:40 was added to a batch reactor in an aqueous batch of ammonia at 2.41 L / hour and 28% concentration.
  • the solution was added at a rate of 0.29 L / hour and the sodium hydroxide solution was brought to a pH of 11.2.
  • the amount of precursor solution, ammonia and sodium hydroxide added was 11.07 L.
  • Comparative Example 2 and Comparative Example 3 were prepared in the same manner as in Comparative Example 1 except that the heat treatment temperature was set to 810 ° C and 790 ° C, respectively.
  • the temperature in the reactor was stirred at 400 rpm while maintaining 46 ° C.
  • the first precursor aqueous solution of 2.5M concentration mixed with nickel sulfate, cobalt sulfate, and manganese sulfate molar ratio in a ratio of 80:10:10 was 2.41L / hour, and 0.29 liter of an aqueous ammonia solution of 28% concentration.
  • the reactor was continuously fed at / hour.
  • a 25% sodium hydroxide aqueous solution was supplied to adjust the pH to maintain a pH of 11.4 ⁇ 11.5.
  • Impeller speed was adjusted to 300 ⁇ 400rpm. 77.22 L of the prepared first precursor aqueous solution, ammonia and sodium hydroxide solution were continuously introduced into the reactor.
  • Batch reactor (batch reactor, 90L) 20 liters of distilled water and 1kg of ammonia was added, and 80.6g of a 2.5M aqueous solution mixed with a nickel sulfate, cobalt sulfate, and manganese sulfate molar ratio of 60:20:20 was added.
  • the motor was stirred at 400 rpm while maintaining the temperature in the reactor at 46 ° C.
  • the first precursor aqueous solution of 2.5M concentration mixed with nickel sulfate, cobalt sulfate, and manganese sulfate molar ratio of 60:20:20 ratio was 2.41 L / hr, and 0.29 liter of aqueous ammonia solution of 28% concentration.
  • the reactor was continuously fed at / hour.
  • a 25% sodium hydroxide aqueous solution was supplied to adjust the pH to maintain a pH of 11.4 ⁇ 11.5.
  • Impeller speed was adjusted to 400 ⁇ 450rpm.
  • 77.22 L of the prepared first precursor aqueous solution, ammonia and sodium hydroxide solution were continuously introduced into the reactor. In consideration of the reactor capacity, the reaction proceeded while the supernatant was discharged at a predetermined time.
  • Particle compositions prepared in Examples and Comparative Examples are shown in Table 1 below.
  • Example 1 in which the barrier layer was applied to the surface of the layer and Example 1 in which the barrier layer was applied to the concentration gradient layer were compared. 2 indicates that primary particle growth is suppressed by applying the barrier layer at about 0.4 to 0.5 ⁇ m as a result of measuring the width average value of the longitudinal primary particles.
  • the concentration of the transition metal in the particles of the active material prepared in Examples 2, 5 and Comparative Example 2 was measured by EDX and compared with the actual designed concentration and the results are shown in FIG. 2.
  • Example 2 which applied the barrier layer after completion
  • the charging and discharging experiments performed between 3 and 4.3 V are shown in FIG. 3.
  • Determination of unreacted lithium is determined by the amount of 0.1M HCl used until pH 4 by pH titration. First, 5 g of the positive electrode active material was added to 100 ml of DIW, stirred for 15 minutes, filtered, 50 ml of the filtered solution was taken, and 0.1 M HCl was added thereto to determine the amount of HCl consumed according to the pH change, thereby determining Q1 and Q2. , Unreacted LiOH and Li 2 CO 3 was calculated according to the formula below.
  • LiOH (wt%) [(Q1-Q2) ⁇ C ⁇ M1 ⁇ 100] / (SPL Size ⁇ 1000)
  • Li 2 CO 3 (wt%) [2 ⁇ Q2 ⁇ C ⁇ M2 / 2 ⁇ 100] / (SPL Size ⁇ 1000)
  • Example 1 in which the barrier layer is applied to the surface of the core layer has a higher optimum heat treatment temperature than Comparative Example 1 in which the barrier layer is not applied, and the residual lithium is low.
  • the positive electrode active material precursor and the positive electrode active material for a lithium secondary battery exhibiting a concentration gradient include a barrier layer between a core having a constant concentration and a shell portion having a concentration gradient, and the prepared cathode active material is formed between the core and the shell. Even when diffusion of transition metal occurs, the industrial use is very useful in that it shows a continuous concentration distribution intended at the design at the interface where core and outer shell meet.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

La présente invention concerne un procédé de production d'un matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration et un matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration produit selon ce dernier, et concerne plus particulièrement un procédé de production d'un matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration et un matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration produit selon ce dernier, le procédé étant caractérisé par la formation d'une couche barrière de façon à maintenir une couche de gradient de concentration y compris en cas de diffusion thermique par un procédé de traitement thermique ultérieur.
PCT/KR2015/007718 2014-12-31 2015-07-24 Procédé de production de précurseur de matériau actif positif et de matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration, et précurseur de matériau actif positif et matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration produits selon ce dernier WO2016108375A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP15875469.7A EP3242348B1 (fr) 2014-12-31 2015-07-24 Procédé de production de précurseur de matériau actif positif et de matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration, et précurseur de matériau actif positif et matériau actif positif pour batteries secondaires au lithium présentant un gradient de concentration produits selon ce dernier
JP2017533200A JP6722673B2 (ja) 2014-12-31 2015-07-24 濃度勾配を示すリチウム二次電池用正極活物質前駆体及び正極活物質を製造する方法、及びこれによって製造された濃度勾配を示すリチウム二次電池用正極活物質前駆体及び正極活物質
CN201580071865.XA CN107112516B (zh) 2014-12-31 2015-07-24 制备锂二次电池用正极活性物质前驱体及正极活性物质的方法、及由此制备的锂二次电池用正极活性物质前驱体及正极活性物质
PL15875469.7T PL3242348T3 (pl) 2014-12-31 2015-07-24 Sposób wytwarzania prekursora dodatniego aktywnego materiału i dodatniego aktywnego materiału do akumulatorów litowych, wykazującego gradient stężenia oraz prekursor dodatniego aktywnego materiału oraz dodatni aktywny materiał do akumulatorów litowych wykazujący gradient stężenia, wytwarzane tym sposobem
US15/630,014 US10749205B2 (en) 2014-12-31 2017-06-22 Method for producing positive active material precursor and positive active material for lithium secondary batteries, exhibiting concentration gradient, and positive active material precursor and positive active material for lithium secondary batteries, exhibiting concentration gradient, produced by same

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US10693136B2 (en) 2016-07-11 2020-06-23 Ecopro Bm Co., Ltd. Lithium complex oxide for lithium secondary battery positive active material and method of preparing the same

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US10693136B2 (en) 2016-07-11 2020-06-23 Ecopro Bm Co., Ltd. Lithium complex oxide for lithium secondary battery positive active material and method of preparing the same

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